KR102550751B1 - Organic-inorganic particle for controlling surface energy, release film including the same, and method of preparing the organic- inorganic particle for controlling surface energy - Google Patents

Abstract

Disclosed are organic/inorganic particles for controlling surface energy, a release film including the same, and a method for manufacturing the organic/inorganic particles for controlling surface energy. The organic-inorganic particles for controlling surface energy may include moieties represented by Formula 1 and Formula 2 below on their surfaces:
<Formula 1>
*-L ₁ -R ₁
<Formula 2>
*-L ₂ -R ₂
In the formula, L ₁ , L ₂ , R ₁ , R ₂ , * are as disclosed in the specification.

Description

Organic-inorganic particle for controlling surface energy, release film including the same, and method of preparing the organic-inorganic particle for controlling surface energy}

It relates to organic/inorganic particles for controlling surface energy, a release film containing the same, and a method for manufacturing the organic/inorganic particles for controlling surface energy.

In general, silicone-based adhesives have heat resistance, weather resistance, flexibility, chemical resistance, and the like, and are recently used in a wide range of applications, such as IT fields such as mobile phones, semiconductors, and displays, as well as general industrial adhesive tapes.

However, since the silicone-based release film using the silicone-based adhesive is completely laminated to the adhesive and is not peeled off, a film coated with a release agent containing a fluorine-based resin is often used. The release agent containing a fluorine-based resin is highly likely to be cured between layers due to residual curing agent after curing, and peeling force and residual adhesion rate are likely to be lowered.

In order to solve this problem, a novel organic-inorganic particle for surface energy control included in the release layer, a release film containing the same with excellent light peelability, residual adhesion, and coating appearance, and a method for manufacturing the organic-inorganic particle for surface energy control there is a demand for

One aspect is to provide novel organic-inorganic particles for controlling surface energy.

Another aspect is to provide a release film excellent in light peelability, residual adhesion, and coating appearance.

Another aspect is to provide a method for producing the organic-inorganic particles for controlling the surface energy.

According to one aspect,

Organic/inorganic particles for controlling surface energy containing moieties represented by Formula 1 and Formula 2 are provided on their surfaces:

<Formula 1>

*-L ₁ -R ₁

during the ceremony,

L ₁ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₁ may be a C1-C20 alkyl group substituted with fluorine;

* may be a part bonded to the particle surface.

<Formula 2>

*-L ₂ -R ₂

during the ceremony,

L ₂ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₂ is a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, or a substituted or unsubstituted C6-C30 cycloalkenyl group , a substituted or unsubstituted C6-C30 bicycloalkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, and a substituted or unsubstituted C6-C30 aryl group,

* may be a part bonded to the particle surface.

According to another aspect,

The base material and the release layer are sequentially located,

The surface energy of the release layer is 24 dyne / cm or less,

The release layer includes organic/inorganic particles,

The organic-inorganic particle is provided with a release film containing moieties represented by Formula 1 and Formula 2 on the surface thereof:

<Formula 1>

*-L ₁ -R ₁

during the ceremony,

L ₁ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₁ may be a C1-C20 alkyl group substituted with fluorine;

* may be a part bonded to the particle surface.

<Formula 2>

*-L ₂ -R ₂

during the ceremony,

L ₂ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₂ is a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, or a substituted or unsubstituted C6-C30 cycloalkenyl group , a substituted or unsubstituted C6-C30 bicycloalkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, and a substituted or unsubstituted C6-C30 aryl group,

* may be a part bonded to the particle surface.

According to another aspect,

adding a silicon alkoxide, a fluorine-containing silane compound, and a silane compound having a functional group to a basic solution and stirring to obtain a mixture;

centrifuging the mixture to obtain a precipitate; and

Including; washing and drying the precipitate to prepare the above-described organic-inorganic particles,

The functional group is a C1-20 alkyl group, a C3-C20 cycloalkyl group, a C2-C20 alkenyl group, a C6-C30 cycloalkenyl group, a C6-C30 bicycloalkenyl group, a C1-C20 alkoxy group, and a C6-C30 group. A method for producing organic/inorganic particles for controlling surface energy, which is at least one selected from C30 aryl groups, is provided.

Organic-inorganic particles for controlling surface energy according to one aspect have a moiety derived from a fluorine-containing silane compound on the surface, and a functional group, for example, a C1-20 alkyl group, a C3-C20 cycloalkyl group, a C2-C20 alkene and a moiety derived from a silane compound having a yl group, a C6-C30 cycloalkenyl group, a C6-C30 bicycloalkenyl group, a C1-C20 alkoxy group, or a C6-C30 aryl group.

The organic/inorganic particles for controlling surface energy have improved compatibility with the fluorine-based release agent included in the release layer and have functionality such as crosslinkability. Therefore, the release film containing the organic/inorganic particles for controlling surface energy has excellent easy peelability, residual adhesion, and coating appearance.

1 is a schematic diagram of organic/inorganic particles for surface energy control according to an embodiment.
2 is a schematic cross-sectional view of a release film according to an embodiment.
3 is a result of analyzing a field emission scanning electron microscope (FE-SEM) image of the organic/inorganic particles synthesized in Example 21.
4 is a result of analyzing FT-IR spectra of organic/inorganic particles synthesized in Example 21, Comparative Example 1, and Comparative Example 3.

Hereinafter, organic/inorganic particles for surface energy control, a release film including the same, and a method for manufacturing the organic/inorganic particles for surface energy control will be described in detail with reference to the embodiments and drawings of the present invention. These examples are only presented as examples to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

In this specification, the term "include" means that other components may be further included without excluding other components unless otherwise stated.

The term "combination of these" as used herein means a mixture or combination of one or more of the recited elements.

The term “and/or” as used herein is meant to include any and all combinations of one or more of the items listed in relation to it. The term "or" as used herein means "and/or". The expression "at least one" or "one or more" in front of elements in this specification does not mean that the list of entire elements can be supplemented and individual elements of the description can be supplemented.

In this specification, when an element is referred to as being disposed “on” or “above” another element, one element may be directly disposed on the other element, or elements intervened between the elements may be present. may exist. On the other hand, when an element is referred to as being disposed “directly on” or “directly over” another element, intervening elements may not be present.

In the present specification, "~ resin", "~ polymer", or/and "~ copolymer" means "~ resin", "~ polymer", "~ copolymer", or/and "~ resin, polymer, Or a derivative of a copolymer" is a concept in a broad sense that includes all.

Organic-inorganic particles for controlling surface energy according to an embodiment may include moieties represented by Formula 1 and Formula 2 below on their surfaces:

<Formula 1>

*-L ₁ -R ₁

during the ceremony,

L ₁ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₁ may be a C1-C20 alkyl group substituted with fluorine;

* may be a part bonded to the particle surface.

<Formula 2>

*-L ₂ -R ₂

during the ceremony,

L ₂ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₂ is a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, or a substituted or unsubstituted C6-C30 cycloalkenyl group , a substituted or unsubstituted C6-C30 bicycloalkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, and a substituted or unsubstituted C6-C30 aryl group,

* may be a part bonded to the particle surface.

1 is a schematic diagram of organic/inorganic particles for surface energy control according to an embodiment.

Referring to FIG. 1 , a moiety 2 represented by Chemical Formula 1 and a moiety 3 represented by Chemical Formula 2 are included on the surface of organic/inorganic particles 1 for controlling surface energy.

The organic/inorganic particles 1 for controlling surface energy have improved compatibility with the fluorine-based release agent included in the release layer and have functionality such as crosslinkability. Therefore, the release film containing the organic/inorganic particles 1 for controlling surface energy has excellent easy peelability, residual adhesion, and coating appearance.

In an exemplary embodiment, the moieties 2 and 3 represented by Formula 1 and Formula 2 may be chemically bonded to the surface of the siloxane-based inorganic polymer particle.

In an exemplary embodiment, the moieties 2 and 3 represented by Formula 1 and Formula 2 may be chemically bonded to the surface of a siloxane-based inorganic polymer particle having a repeating unit structure represented by Formula 3 below. :

<Formula 3>

during the ceremony,

R _a and R _b may be each independently a hydrogen atom or an unsubstituted C1-C5 alkyl group,

p can be an integer from 1 to 3000,

* may be a moiety represented by Formula 1 and Formula 2 is bonded.

In an exemplary embodiment, the siloxane-based inorganic polymer particle may include a cyclosiloxane-based polymer particle represented by Chemical Formula 4:

<Formula 4>

during the ceremony,

R' may be an unsubstituted C1-C5 alkoxy group,

* may be a moiety represented by Formula 1 and Formula 2 is bonded.

In an exemplary embodiment, R ₁ may be a C1-C10 alkyl group substituted with fluorine.

In an exemplary embodiment, R ₂ is a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C2-C10 alkenyl group. a C6-C10 cycloalkenyl group, a substituted or unsubstituted C6-C20 bicycloalkenyl group, a substituted or unsubstituted C1-C10 alkoxy group, and a substituted or unsubstituted C6-C10 aryl group. can

The diameter of the organic-inorganic particle 1 may be 1 μm or less. For example, the diameter of the organic/inorganic particles 1 may be 1 nm to 900 nm, 5 nm to 800 nm, 10 nm to 700 nm, 20 nm to 700 nm, or 30 nm to 700 nm. nm or 40 nm to 600 nm or 50 nm to 600 nm or 60 nm to 600 nm or 70 nm to 600 nm or 80 nm to 600 nm or 90 nm to 600 nm 100 nm to 600 nm, 100 nm to 500 nm, 100 nm to 400 nm, or 100 nm to 300 nm. The shape of the organic-inorganic particle 1 is not limited, but may be, for example, a spherical shape or a shape close to a spherical shape. The shape close to the sphere may include, for example, an oval shape.

In the release film according to another embodiment, a substrate and a release layer are sequentially positioned, the release layer has a surface energy of 24 dyne/cm or less, the release layer includes organic/inorganic particles 1, and the organic/inorganic The particle may include moieties represented by Formula 1 and Formula 2 below on its surface:

<Formula 1>

*-L ₁ -R ₁

during the ceremony,

L ₁ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₁ may be a C1-C20 alkyl group substituted with fluorine;

* may be a part bonded to the particle surface.

<Formula 2>

*-L ₂ -R ₂

during the ceremony,

L ₂ may be selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;

R ₂ is a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, or a substituted or unsubstituted C6-C30 cycloalkenyl group , a substituted or unsubstituted C6-C30 bicycloalkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, and a substituted or unsubstituted C6-C30 aryl group,

* may be a part bonded to the particle surface.

The organic-inorganic particle 1 includes moieties 2 and 3 represented by Chemical Formula 1 and Chemical Formula 2 on its surface. These organic/inorganic particles 1 can improve compatibility with the fluorine-based release agent included in the release layer and have functionality such as crosslinkability while controlling surface energy to 24 dyne/cm or less. Therefore, the release film containing the organic/inorganic particles 1 is excellent in light peelability, residual adhesion, and coating appearance.

In an exemplary embodiment, the moieties 2 and 3 represented by Formula 1 and Formula 2 may be chemically bonded to the surface of the siloxane-based inorganic polymer particle.

In an exemplary embodiment, the moieties 2 and 3 represented by Formula 1 and Formula 2 may be chemically bonded to the surface of a siloxane-based inorganic polymer particle having a repeating unit structure represented by Formula 3 below. :

<Formula 3>

during the ceremony,

R _a and R _b may be each independently a hydrogen atom or an unsubstituted C1-C5 alkyl group,

p can be an integer from 1 to 3000,

* may be a moiety represented by Formula 1 and Formula 2 is bonded.

In an exemplary embodiment, the siloxane-based inorganic polymer particle may include a cyclosiloxane-based polymer particle represented by Chemical Formula 4:

<Formula 4>

during the ceremony,

R' may be an unsubstituted C1-C5 alkoxy group,

* may be a moiety represented by Formula 1 and Formula 2 is bonded.

As the substrate used in the present invention, a known substrate film or sheet known as a release film substrate may be used. For example, a polyester-based resin film can be used as the substrate. As the polyester-based resin, a known base film commonly used in the release film field may be used. For example, the polyester base film disclosed in Korean Patent Registration No. 10-1268584, Korean Patent Publication No. 2012-45213, and Korean Patent Publication No. 2012-99546 may be used. However, in one embodiment of the present invention, in order to explain only the characteristics of the present invention, the polyester base film is described without limitation, but it should be understood that the known technical characteristics of the polyester base film are included. .

The polyester base film may include polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate.

The polyester resin forming the base film may be polyester obtained by polycondensation of aromatic dicarboxylic acid and aliphatic glycol, and aromatic dicarboxylic acid is isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalendica Riboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (eg, P-oxybenzoic acid, etc.) may be used, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4- Cyclohexanedimethanol, neopentyl glycol, etc. can be used. Such a polyester-based resin may use a combination of two or more of a dicarboxylic acid component and a glycol component, and a copolymer containing a third component is also possible.

In addition, the polyester base film may be a uniaxial or biaxially oriented film having high transparency and excellent productivity and processability. Polyethylene terephthalate (PET) or polyethylene-2,6-naphthalenedicarboxylate (PEN) may be used as the polyester-based base film.

In addition, the polyester-based base film may contain particles in order to impart excellent inter-roll running properties, and as long as the added particles can exhibit excellent sliding properties, they can be used without limitation.

Examples of such particles may include particles of silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium oxide, and the like. Although not limited to, for example, any of spherical, massive, rod, and plate-shaped particles may be used.

In addition, the hardness, specific gravity and color of the particles are not limited, but two or more types may be used in parallel if necessary, and the average particle diameter of the particles used may be 0.1 to 5 μm, for example, in the range of 0.1 to 2 μm. that can be used At this time, if the average particle diameter of the particles is less than 0.1 μm, aggregation between particles may occur, resulting in poor dispersion, and if the average particle diameter of the particles exceeds 5 μm, the surface roughness characteristics of the film deteriorate, resulting in poor coating during post-processing. may occur.

In addition, when particles are included in the polyester-based base film, the content of the particles may be 0.01 to 5% by weight, for example, 0.01 to 3% by weight based on the total weight of the polyester-based base film. If the content of the particles is less than 0.01% by weight, the sliding properties of the polyester film may deteriorate, resulting in poor rolling characteristics between rolls, and if the content of the particles exceeds 5% by weight, the surface smoothness of the film may be deteriorated.

The thickness of the polyester-based base film is not limited, but may be 30 to 125 μm.

If the polyester-based base film is too thin, less than 30um, there is a concern that it may be deformed by heat treatment during processing, and if it is too thick, more than 125um, heat may not be sufficiently transmitted and there may be a problem in curing.

The release layer of the release film according to one embodiment may have a surface energy of 24 dyne/cm or less. Due to such a low surface energy, the release film including the release layer can implement light peelability with low peel force.

The release layer includes the aforementioned organic-inorganic particles.

In the release layer, peaks may appear in a wavelength range of 600 to 900 cm ^-1 and a wavelength range of 1000 to 1250 cm ^-1 in the IR spectrum.

The release layer may further include a polymer or copolymer including fluorinated polysiloxane.

The fluorinated polysiloxane may include organopolysiloxane represented by Chemical Formula 5 below:

<Formula 5>

<Formula 6>

<Formula 7>

during the ceremony,

R ₃ may be a substituted or unsubstituted C1~C10 monovalent hydrocarbon group or a substituted or unsubstituted C2~C10 alkenyl group;

R ₄ may be a substituted or unsubstituted C1~C10 monovalent hydrocarbon group, a substituted or unsubstituted C2~C10 alkenyl group, or hydrogen;

R ₅ may be a fluorine-containing alkyl group represented by Chemical Formula 5, a fluorine-containing ether group represented by Chemical Formula 6, or a combination thereof;

n may be an integer of 1 to 8, m may be an integer of 1 to 5;

p may be an integer from 1 to 5, q may be 0 or 1, r may be 0, 1 or 2, and v may be an integer from 1 to 5;

A may be an oxygen atom or a single bond;

x, y, z may each be an integer of 1 or greater;

* may be a binding site with a neighboring atom;

However, at least one of R ₃ R ₄ may be a substituted or unsubstituted C2-C10 alkenyl group.

If necessary, the fluorinated polysiloxane may be a blend of organopolysiloxane represented by Chemical Formula 5 and organopolysiloxane represented by Chemical Formula 8 below, or an organopolysiloxane represented by Chemical Formula 5 and an organopolysiloxane represented by Chemical Formula 8. Organopolysiloxanes can be linked copolymers:

<Formula 8>

<Formula 9>

during the ceremony,

R' ₁ may be a substituted or unsubstituted C1~C10 monovalent hydrocarbon group or a substituted or unsubstituted C2~C10 alkenyl group;

R' ₂ may be a fluorine-containing ether group represented by Chemical Formula 9;

n' may be an integer of 1 to 8, m' may be an integer of 3 to 17;

* may be a binding site with a neighboring atom.

For example, the weight ratio between the organopolysiloxane represented by Chemical Formula 5 and the organopolysiloxane represented by Chemical Formula 8 may range from 10:1 to 1:10.

The release layer may further include at least one of hydrogen polysiloxane and an acid catalyst.

The hydrogen polysiloxane may include at least one of an addition reaction type siloxane resin, a condensation reaction type siloxane resin, and an ultraviolet curing type siloxane resin. The hydrogen polysiloxane may be in the form of one of linear, branched, or cyclic, and may be in the form of a mixture thereof. The hydrogen polysiloxane is not limited in viscosity or molecular weight, but must have good compatibility with the organopolysiloxane described above, and the hydrogen polysiloxane may not contain a fluorine group. However, the hydrogen polysiloxane may contain the same fluorine-containing alkyl group or/and fluorine-containing ether group as the organopolysiloxane described above.

The content of the hydrogen polysiloxane may be 1.0 to 10.0% by weight based on the total weight of the composition forming the release layer.

The acid catalyst may use one or more metals or amphoteric elements selected from Groups 4 to 14 elements, for example, one or more selected from Rh, Pt, Sn, Ti, Pd, Ir, W, and Co. can be used For example, the acid catalyst may include a platinum chelate catalyst.

If necessary, the release layer may further contain additives for imparting various functions such as a reaction modifier and an antistatic agent.

The release layer may have a thickness of 0.03 to 3.0 μm. If the thickness of the release layer is less than 0.01 um, the release layer coverage is not good, and if it exceeds 3 um, a large amount of heat is required during curing, which may cause thermal deformation of the base film.

2 is a schematic cross-sectional view of a release film 100 according to an embodiment.

Referring to FIG. 2 , the release film 120 according to one embodiment has a structure in which a substrate 100 and a release layer 110 are sequentially positioned.

The release film 120 according to one embodiment can provide a release film excellent in light peelability, residual adhesion, and coating appearance.

The peel force of the release film 120 may be 24 gf/25 mm or less.

The residual adhesion rate of the release film 120 may be 89% or more.

If the residual adhesion rate of the release film 120 is less than 89%, the release layer is insufficiently cured, so that the release agent is transferred to the adhesive layer and the adhesiveness of the adhesive is deteriorated.

A method for preparing organic/inorganic particles for controlling surface energy according to another embodiment includes adding silicon alkoxide, a fluorine-containing silane compound, and a silane compound having a functional group to a basic solution and stirring to obtain a mixture; centrifuging the mixture to obtain a precipitate; And washing and drying the precipitate to prepare the above-described organic-inorganic particles; including,

The functional group is a C1-20 alkyl group, a C3-C20 cycloalkyl group, a C2-C20 alkenyl group, a C6-C30 cycloalkenyl group, a C6-C30 bicycloalkenyl group, a C1-C20 alkoxy group, and a C6-C30 group. It may be one or more selected from C30 aryl groups.

For example, the basic solution may be a mixture of ammonia water or a mixture of ammonia water and an alcohol solvent. For example, the alcohol solvent may include ethanol.

For example, the fluorine-containing silane compound may include one or more of the compounds represented by A-1 to A-5 below:

A-1 A-2

A-3

A-4

A-5

For example, the silane compound having the functional group may include one or more of the compounds represented by the following B-1 to B-14:

B-1 B-2

B-3

B-4 B-5

B-6 B-7

B-8 B-9

B-10 B-11

B-12 B-13

B-14

The weight ratio of the fluorine-containing silane compound to the silane compound having a functional group may be 1:0.05 to 1:2. When the weight ratio of the fluorine-containing silane compound to the silane compound having a functional group is within the above range, the moieties represented by Chemical Formulas 1 and 2 are disposed on the surface of the organic/inorganic particles without aggregation, resulting in better compatibility with the fluorine-based release agent. Not only can it be improved, but also functionality such as crosslinkability can be further improved. Therefore, the release film containing the organic/inorganic particles is very excellent in light peelability, residual adhesion, and coating appearance.

In the step of obtaining a precipitate by centrifuging the mixture, centrifugation may be performed one or more times, for example, at 3000 to 7000 rpm for 1 to 30 minutes. The aforementioned organic/inorganic particles may be prepared by adding an alcohol solvent or the like to the precipitate, performing the centrifugation process as described above, and drying at room temperature.

A method for manufacturing a release film according to another embodiment includes preparing a substrate; preparing the aforementioned organic/inorganic particles; and forming a release layer by coating and drying a composition for forming a release layer including a polymer or copolymer including a fluorinated polysiloxane and the organic/inorganic particles on at least one surface of the substrate, thereby preparing the release film; can include

The release film prepared by the method for manufacturing a release film according to an embodiment can provide a release film excellent in light peelability, residual adhesion, and coating appearance.

At this time, as the solvent used in the composition for forming a release layer, any solvent capable of dispersing solids of the composition for forming a release layer and applied onto a substrate may be used without limitation. If the total solid content of the composition for forming a release layer is less than 0.5% by weight, a uniform release layer may not be formed, causing problems such as incomplete separation between the silicone-based adhesive layer and the release film, and 10% by weight If it exceeds , the viscosity of the composition for forming the release layer is high, and leveling unevenness may occur, and thus the thickness uniformity of the release layer may be deteriorated.

Examples of the solvent used in the release layer-forming composition include aromatic hydrocarbon-based solvents such as toluene and xylene; aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin; Hydrocarbon solvents, such as industrial gasoline (rubber gasoline etc.), petroleum benzene, and solvent naphtha; Acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonylacetone, cyclohexanone, etc. ketone solvents; ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; solvents having ester and ether moieties such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; siloxane-based solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decanemethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; fluorine-based solvents such as trifluorotoluene, hexafluoroxylene, methyl nonafluorobutyl ether, and ethyl nonafluorobutyl ether; or a mixed solvent thereof may be used. For example, a mixed solvent of heptane and methyl isobutyl ketone may be used as the solvent used in the composition for forming the release layer.

As a method of applying the composition for forming a release layer on a substrate, an offline coating method usable in the art, such as bar coating, gravure coating, and die coating, may be used. The energy source for curing the composition for forming a release layer is not particularly limited, but heat treatment, ultraviolet irradiation, or electron beam irradiation may be used, and these may be used alone or in combination, but heat treatment alone or combined heat and ultraviolet light may be used. can

As used herein, "substitution" is derived by exchanging one or more hydrogen atoms or functional groups in an unsubstituted parent group. Unless otherwise stated, when a functional group is considered "substituted", it means that the functional group is an alkyl group of 1 to 40 carbon atoms, an alkenyl group of 2 to 40 carbon atoms, an alkynyl group of 2 to 40 carbon atoms, a cycloalkyl group of 3 to 40 carbon atoms It means that it is substituted with one or more substituents selected from an alkyl group, a cycloalkenyl group having 3 to 40 carbon atoms, and an aryl group having 7 to 40 carbon atoms. When a functional group is described as "optionally substituted", it is meant that the functional group may be substituted with the substituents described above.

In the present specification, examples of the C1-C10 monovalent hydrocarbon group include a straight-chain alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a decyl group; branched alkyl groups such as isopropyl group, tert-butyl group, neopentyl group, and hexyl group; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; aryl groups such as vinyl, henyl and tolyl groups; aralkyl groups such as benzyl and phenethyl groups; means etc. Among these, it may be an alkyl group in consideration of the ease of procurement of raw materials, and may be a methyl group or an ethyl group in consideration of the usefulness of the product.

In the present specification, the C1-C20 alkyl group includes, for example, a straight-chain alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a decyl group; an isopropyl group, a tert-butyl group, a neopentyl group, and the like. Among these, it may be an alkyl group in consideration of the ease of procurement of raw materials, and may be a methyl group or an ethyl group in consideration of the usefulness of the product.

In the present specification, the C1-C5 alkylene group includes, for example, a straight-chain alkylene group such as a methylene group or an ethylene group; An isopropylene group, a tert-butylene group, and the like may be included.

In the present specification, a C3-C20 cycloalkyl group means a univalent radical formed by removing one hydrogen atom from a cycloalkane. Non-limiting examples of the cycloalkyl group include a cycloalkyl group, a cycloethyl group, a cyclopropyl group, or a cyclobutyl group.

In this specification, a C2~C20 alkenyl group means a branched or unbranched hydrocarbon having at least one carbon-carbon double bond. Non-limiting examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, an isopropenyl group, an isobutenyl group, and the like.

In the present specification, the C3-C20 cycloalkenyl group includes, for example, a cyclomethylene group, a cycloethylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, or a cycloheptylene group. there is.

In this specification, a C6-C30 bicycloalkenyl group means a bicycloalkyl group containing one or more unsaturated carbon-carbon bonds. Non-limiting examples of the bicycloalkenyl group may include a bicyclo[2.2.1]hept-5-en-2-yl group and the like.

In the present specification, the C1~C20 alkoxy group means an oxygen-bonded alkyl group. Non-limiting examples of the alkoxy group include a methoxy group, an ethoxy group, and the like.

In the present specification, the C6-C30 aryl group is used alone or in combination to mean an aromatic system containing one or more rings. Non-limiting examples of aryl groups include phenyl, naphthyl, and the like.

Hereinafter, the configuration of the present invention and its effects will be described in more detail through Examples and Comparative Examples. However, these examples are intended to explain the present invention in more detail, and it will be obvious that the scope of the present invention is not limited to these examples.

[Example]

(organic/inorganic particle synthesis)

Example 1: Organic/Inorganic Particles P-1

As a basic solution, a mixed solution of 12 ml of ammonia water (28%) and 10 ml of ethanol was prepared. At room temperature, 4 mmol of tetraethyl orthosilicate (TEOS) as a silicon alkoxide and the following compound A-1 (trimethoxy (3,3,3-trifluoropropyl) silane as a fluorine-containing silane compound) were added to the mixed solution at room temperature. A solution containing 1 mmol of Trimethoxy(3,3,3-trifluoropropyl)silane, 1 mmol of the following compound B-1 (trimethoxymethylsilane) as a silane compound having a functional group, and 10 ml of ethanol was added dropwise, A mixture was obtained by stirring for 10 minutes. The mixture was centrifuged at 5000 rpm for 3 minutes to obtain a precipitate. 10 ml of ethanol was added to the precipitate, and further centrifugation was performed at 5000 rpm for 3 minutes to wash and dry to obtain white powdery organic/inorganic particles P-1.

A-1 B-1

Example 2: Organic/Inorganic Particles P-2

As the fluorine-containing silane compound, the following A-2 compound (triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane; Triethoxy (3,3,4,4, 5,5,6,6,6-nonafluorohexyl)silane) Organic-inorganic particles P-2 were obtained in the same manner as in Example 1, except that 1 mmol was used.

A-2

Example 3: Organic/Inorganic Particles P-3

As the fluorine-containing silane compound, the following compound A-3 (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) Organic-inorganic particles in the same manner as in Example 1 except for using 1 mmol Got P-3.

A-3

Example 4: Organic/Inorganic Particles P-4

As the fluorinated silane compound, the following A-4 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hepta) decafluorodecyl)silane; Triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane) 1 mmol Except for the use, organic-inorganic particles P-4 were obtained in the same manner as in Example 1.

A-4

Example 5: Organic/Inorganic Particles P-5

As the fluorine-containing silane compound, the following A-5 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11 , 12, 12, 12-henicosafluorodecyl) silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11 ,11,12,12,12-henicosafluorododecyl))silane) to obtain organic-inorganic particles P-5 in the same manner as in Example 1, except that 1 mmol was used.

A-5

Example 6: Organic/Inorganic Particles P-6

As the fluorine-containing silane compound, the A-2 compound (triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane; Triethoxy (3,3,4,4, 5,5,6,6,6-nonafluorohexyl)silane) 1 mmol and the following B-2 compound (triethoxyhexylsilane) as a silane compound having a functional group (triethoxyhexylsilane) 1 mmol, except for using Example 1 and Organic-inorganic particles P-6 were obtained in the same manner.

B-2

Example 7: Organic/Inorganic Particles P-7

As the fluorine-containing silane compound, the A-2 compound (triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane; Triethoxy (3,3,4,4, 5,5,6,6,6-nonafluorohexyl)silane) as in Example 1, except for using 1 mmol of B-3 compound (triethoxydecylsilane) as a silane compound having a functional group and 1 mmol of Organic-inorganic particles P-7 were obtained in the same manner.

B-3

Example 8: Organic/Inorganic Particles P-8

As the fluorine-containing silane compound, the A-2 compound (triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane; Triethoxy (3,3,4,4, Example 1, except for using 1 mmol of 5,5,6,6,6-nonafluorohexyl)silane) and 1 mmol of the following B-4 compound (triethoxyisobutylsilane) as a silane compound having a functional group. Organic-inorganic particles P-8 were obtained in the same manner as above.

B-4

Example 9: Organic-inorganic particles P-9

As the fluorine-containing silane compound, the A-2 compound (triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane; Triethoxy (3,3,4,4, 5,5,6,6,6-nonafluorohexyl)silane) 1 mmol and the following B-5 compound as a silane compound having a functional group (triethoxy(3,3-dimethylbutyl)silane; Triethoxy(3,3-dimethylbutyl) Except for using 1 mmol of silane), organic/inorganic particles P-9 were obtained in the same manner as in Example 1.

B-5

Example 10: Organic/Inorganic Particles P-10

As the fluorine-containing silane compound, the A-2 compound (triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl) silane; Triethoxy (3,3,4,4, 5,5,6,6,6-nonafluorohexyl)silane) 1 mmol and the following B-6 compound as a silane compound having a functional group (triethoxy (2,4,4-trimethylpentyl) silane; Triethoxy (2,4, Organic/inorganic particles P-10 were obtained in the same manner as in Example 1, except that 1 mmol of 4-trimethylpentyl)silane) was used.

B-6

Example 11: Organic/Inorganic Particles P-11

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-2 compound (triethoxyhexylsilane; Triethoxyhexylsilane) 1 mmol Except for using, organic-inorganic particles P-11 were obtained in the same manner as in Example 1.

Example 12: Organic/Inorganic Particles P-12

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-3 compound (triethoxydecylsilane; Triethoxydecylsilane) 1 mmol Except for using, organic-inorganic particles P-12 were obtained in the same manner as in Example 1.

Example 13: Organic/Inorganic Particles P-13

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the above B-4 compound (triethoxyisobutylsilane; Triethoxyisobutylsilane) 1 Except for using mmol, organic-inorganic particles P-13 were obtained in the same manner as in Example 1.

Example 14: Organic/Inorganic Particles P-14

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the above B-5 compound (triethoxy(3,3-dimethylbutyl) ) Silane: Organic/inorganic particles P-14 were obtained in the same manner as in Example 1, except that 1 mmol of triethoxy(3,3-dimethylbutyl)silane was used.

Example 15: Organic/Inorganic Particles P-15

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the above B-6 compound (triethoxy(2,4,4- Organic/inorganic particles P-15 were obtained in the same manner as in Example 1, except that 1 mmol of trimethylpentyl)silane; Triethoxy(2,4,4-trimethylpentyl)silane was used.

Example 16: Organic/Inorganic Particles P-16

As the fluorine-containing silane compound, the A-4 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hepta) decafluorodecyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane) 1 mmol and Organic-inorganic particles P-16 were obtained in the same manner as in Example 1, except that 1 mmol of the compound B-2 (triethoxyhexylsilane) was used.

Example 17: Organic/Inorganic Particles P-17

As the fluorine-containing silane compound, the A-4 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hepta) decafluorodecyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane) 1 mmol and Organic-inorganic particles P-17 were obtained in the same manner as in Example 1, except that 1 mmol of the compound B-3 (triethoxydecylsilane) was used.

Example 18: Organic/Inorganic Particles P-18

As the fluorine-containing silane compound, the A-5 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11 , 12, 12, 12-henicosafluorodecyl) silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11 ,11,12,12,12-henicosafluorododecyl)) silane) 1 mmol and the B-2 compound (triethoxyhexylsilane) 1 mmol, except for using, organic inorganic particles in the same manner as in Example 1 Got P-18.

Example 19: Organic/Inorganic Particles P-19

As the fluorine-containing silane compound, the A-5 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11 , 12, 12, 12-henicosafluorodecyl) silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11 ,11,12,12,12-henicosafluorododecyl)) silane) 1 mmol and the B-3 compound (triethoxydecylsilane) 1 mmol, except for using, organic inorganic particles in the same manner as in Example 1 Got P-19.

Example 20: Organic/Inorganic Particles P-20

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following compound B-7 (triethoxyvinylsilane; Triethoxyvinylsilane) 1 mmol Except for using, organic-inorganic particles P-20 was obtained in the same manner as in Example 1.

B-7

Example 21: Organic/Inorganic Particles P-21

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following compound B-8 (triethoxy (5-hexenyl) silane) Organic/inorganic particles P-21 were obtained in the same manner as in Example 1, except that 1 mmol of triethoxy(5-hexenyl)silane was used.

B-8

Example 22: Organic/Inorganic Particles P-22

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following compound B-9 (triethoxy (bicyclo[2.2.1 ]Hept-5-en-2-yl)silane; With or without Triethoxy (bicyclo[2.2.1]hept-5-en-2-yl)silane) in the same manner as in Example 1, except that 1 mmol was used. A group particle P-22 was obtained.

B-9

Example 23: Organic/Inorganic Particles P-23

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following B-10 compound (triethoxy(4-(bicyclo[ 2.2.1]hept-5-en-2-yl)butyl)silane; Triethoxy(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)silane) except for using 1 mmol In the same manner as in Example 1, organic-inorganic particles P-23 were obtained.

B-10

Example 24: Organic/Inorganic Particles P-24

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following B-11 compound (triethoxy (2- (3-cyclo Hexenyl) ethyl) silane; Organic-inorganic particles P-24 were obtained in the same manner as in Example 1, except that 1 mmol of Triethoxy (2- (3-cyclohexenyl) ethyl) silane was used.

B-11

Example 25: Organic/Inorganic Particles P-25

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following compound B-12 (triethoxyphenylsilane; Triethoxyphenylsilane) 1 mmol Except for using, organic-inorganic particles P-25 were obtained in the same manner as in Example 1.

B-12

Example 26: Organic/Inorganic Particles P-26

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following B-13 compound (triethoxy (ρ-tolyl) silane; Organic-inorganic particles P-26 were obtained in the same manner as in Example 1, except that 1 mmol of triethoxy(ρ-tolyl)silane was used.

B-13

Example 27: Organic/Inorganic Particles P-27

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the following B-14 compound (triethoxy (1-naphthalenyl) Silane: Organic-inorganic particles P-27 were obtained in the same manner as in Example 1, except that 1 mmol of triethoxy(1-naphthalenyl)silane was used.

B-14

Example 28: Organic/Inorganic Particles P-28

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-2 compound (triethoxyhexylsilane; Triethoxyhexylsilane) 0.25 mmol Except for using, organic-inorganic particles P-28 were obtained in the same manner as in Example 1.

Example 29: Organic-inorganic particles P-29

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-2 compound (triethoxyhexylsilane; Triethoxyhexylsilane) 0.5 mmol Except for using, organic-inorganic particles P-29 were obtained in the same manner as in Example 1.

Example 30: Organic/Inorganic Particles P-30

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-2 compound (triethoxyhexylsilane; Triethoxyhexylsilane) 2 mmol Except for using, organic-inorganic particles P-30 was obtained in the same manner as in Example 1.

Example 31: Organic/Inorganic Particles P-31

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the above B-8 compound (triethoxy (5-hexenyl) silane) Organic/inorganic particles P-31 were obtained in the same manner as in Example 1, except that 0.25 mmol of triethoxy(5-hexenyl)silane was used.

Example 32: Organic/Inorganic Particles P-32

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the above B-8 compound (triethoxy (5-hexenyl) silane) Organic/inorganic particles P-32 were obtained in the same manner as in Example 1, except that 0.5 mmol of triethoxy(5-hexenyl)silane was used.

Example 33: Organic-inorganic particles P-33

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the above B-8 compound (triethoxy (5-hexenyl) silane) Organic/inorganic particles P-33 were obtained in the same manner as in Example 1, except that 2 mmol of triethoxy(5-hexenyl)silane was used.

Example 34: Organic/Inorganic Particles P-34

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-12 compound (triethoxyphenylsilane; Triethoxyphenylsilane) 0.25 mmol Except for using, organic-inorganic particles P-34 were obtained in the same manner as in Example 1.

Example 35: Organic-inorganic particles P-35

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-12 compound (triethoxyphenylsilane; Triethoxyphenylsilane) 0.5 mmol Except for using, organic-inorganic particles P-35 were obtained in the same manner as in Example 1.

Example 36: Organic-inorganic particles P-36

As the fluorine-containing silane compound, the A-3 compound (triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane) 1 mmol and the B-12 compound (triethoxyphenylsilane; Triethoxyphenylsilane) 2 mmol Except for using, organic-inorganic particles P-36 were obtained in the same manner as in Example 1.

Comparative Example 1: Organic/Inorganic Particles P-37

At room temperature, a solution obtained by adding 4 mmol of tetraethyl orthosilicate (TEOS) as a silicon alkoxide and 10 ml of ethanol was added dropwise to the mixed solution and stirred for 10 minutes to obtain a mixture. Example 1 and In the same manner, organic/inorganic particles P-37 having no fluorine or functional moiety on the surface were obtained.

Comparative Example 2: Organic/Inorganic Particles P-38

At room temperature, 4 mmol of tetraethyl orthosilicate (TEOS) as a silicon alkoxide and the A-2 compound (triethoxy (3,3,4,4,5,5, A solution containing 1 mmol of 6,6,6-nonafluorohexyl)silane; Triethoxy (3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane and 10 ml of ethanol was added dropwise. and stirred for 10 minutes to obtain organic/inorganic particles P-38 containing no functional moiety on the surface in the same manner as in Example 1, except that a mixture was obtained.

Comparative Example 3: Organic/Inorganic Particles P-39

At room temperature, 4 mmol of tetraethyl orthosilicate (TEOS) as a silicon alkoxide and the A-3 compound (triethoxy (3,3,4,4,5,5, 6,6,7,7,8,8,8-tridecafluorooctyl)silane; Triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctyl)silane) 1 mmol and 10 ml of ethanol were added dropwise and stirred for 10 minutes to obtain a mixture, in the same manner as in Example 1, except that the organic-inorganic particle P having no functional moiety on the surface I got -39.

Comparative Example 4: Organic/Inorganic Particles P-40

At room temperature, 4 mmol of tetraethyl orthosilicate (TEOS) as a silicon alkoxide and the A-4 compound (triethoxy (3,3,4,4,5,5, 6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane; Triethoxy(3,3,4,4,5,5,6,6,7, 7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane) 1 mmol, and a solution to which 10 ml of ethanol were added dropwise, and stirred for 10 minutes to obtain a mixture, except that a mixture was obtained. In the same manner, organic/inorganic particles P-40 having no functional group moiety on the surface were obtained.

(Manufacture of release film)

Example 37: release film

A 30 μm thick polyester film (Toray Advanced Materials, XD500P) was prepared.

Separately, 100 parts by weight of organopolysiloxane represented by the following formula 5 containing a fluorine-containing alkyl group represented by the following formula 6 (manufactured by Dow Chemical, Q2-7785), hydrogen polysiloxane (manufactured by Dow Chemical, Q2-7560) 3 parts by weight, 1 part by weight of a platinum chelate catalyst (SYL-OFF 4000, manufactured by Dow Chemical) was diluted in a mixed solvent of heptane and methyl isobutyl ketone (5: 1 volume ratio) to prepare a composition having a total solid content of 5% by weight. Then, a composition for forming a release layer was prepared by blending the organic/inorganic particles P-1 synthesized in Example 1 in an amount of 1% by weight based on the total solid content.

A release film was prepared by applying the composition for forming a release layer on one side of the polyester film and heat-treating for 2 minutes in a hot air dryer at 150 ° C to form a release layer having a thickness of 0.3 μm:

<Formula 5>

<Formula 6>

during the ceremony,

R ₃ is a vinyl group, R ₄ is a methyl group, R ₅ is a fluorine-containing alkyl group represented by Formula 6;

n=4 and m is 2;

The weight average molecular weight (Mw) is about 175,000.

* is a binding site with a neighboring atom.

Examples 38 to 72: release film

A release film was manufactured in the same manner as in Example 37, except that the organic/inorganic particles synthesized in Examples 2 to 36 were used instead of the organic/inorganic particles synthesized in Example 1.

Comparative Examples 5 to 8: Release Film

A release film was manufactured in the same manner as in Example 37, except that the organic/inorganic particles synthesized in Comparative Examples 1 to 4 were used instead of the organic/inorganic particles synthesized in Example 1.

Analysis Example 1: Field Emission Scanning Electron Microscope (FE-SEM) Experiment

Field emission scanning electron microscope images of the organic/inorganic particles synthesized in Example 21 were analyzed. A scanning electron microscope (S4800, Hitach) was used, and experiments were performed at x30.0k magnification. The results are shown in Figure 3.

Referring to FIG. 3, it can be seen that the organic/inorganic particles synthesized in Example 21 are spherical particles having a diameter of about 100 to 300 nm.

Analysis Example 2: FT-IR spectrum

FT-IR spectra were analyzed for the organic/inorganic particles synthesized in Example 21, Comparative Example 1, and Comparative Example 3. FT-IR spectrum analysis was performed using PerkinElmer's FT-IR. The results are shown in FIG. 4 .

Referring to FIG. 4 , the organic/inorganic particles synthesized in Example 21 and Comparative Example 3 showed peaks in the wavelength range of 600 to 900 cm ^-1 and the wavelength range of 1000 to 1250 cm ^-1 . The organic/inorganic particles synthesized in Comparative Example 1 did not show peaks in the wavelength range of 600 to 900 cm ^-1 and the wavelength range of 1000 to 1250 cm ^-1 . From this, it can be confirmed that the organic/inorganic particles synthesized in Example 21 and Comparative Example 3 each have a moiety derived from a fluorine-containing silane compound and a silane compound having a functional group on the surface.

Evaluation Example 1: Evaluation of physical properties

The physical properties of the release films prepared in Examples 37 to 72 and Comparative Examples 5 to 8 were evaluated in the following manner, and the results are shown in Table 1.

(1) Peeling force of release film

Samples were prepared by cutting each release film into a size of 500 mm x 1500 mm. The samples were stored for 24 hours at 25°C and 65% RH. Thereafter, silicone-based adhesive tape (Nitto, 903UL) was pressed on the release layer of the samples at 50°C and a load of 20 g/cm ² for 24 hours, and then, using a cheminstrument AR-2000 device, 250 mm at 180° and a speed of 0.3 mpm. The peel force of the size x 1500 mm was measured. At this time, the peel force was obtained by calculating the average value after measuring 5 times.

(2) Residual adhesion rate of release film

Samples were prepared by cutting each release film into a size of 500 mm x 1500 mm. The samples were stored for 24 hours at 25°C and 65% RH. After compressing an adhesive tape (Nitto, 31B) on the release layer of the samples at room temperature under a load of 20 g/cm ² for 24 hours, the adhesive tape adhered to the release layer was collected without contamination. The adhesive tape was adhered to a surface of a polyethylene terephthalate film having a flat and clean surface. The adhesive tape adhered to the surface of the polyethylene terephthalate film was pressed back and forth once with a 2 kg tape roller (ASTMD-1000-55T), and 250 mm x 1500 mm at 180° and 0.3 mpm speed using a cheminstrument AR-2000 machine. After measuring the peel force of the size, it was substituted into the following formula 2 to obtain the residual adhesion rate.

[Equation 1]

Residual adhesion rate (%) = [(peel force of the adhesive tape peeled off after being adhered to the release layer)/(peel force of the adhesive tape not in contact with the release layer) x 100]

(3) Evaluation of release layer appearance

Each release film was prepared as an A4-sized sample, placed on a black-bottomed evaluation board, and cratering and appearance defects of the release layer were confirmed and recorded under a fluorescent light.

o: less than 2 craters

△: 3 to 5 craters

X: greater than 5 craters

Peel force (gf/25 mm) Residual adhesion rate (%) Appearance evaluation Example 37 23 92 O Example 38 23 91 O Example 39 22 91 O Example 40 22 91 O Example 41 22 89 O Example 42 23 91 O Example 43 23 91 O Example 44 22 92 O Example 45 22 91 O Example 46 23 92 O Example 47 23 92 O Example 48 23 91 O Example 49 23 91 O Example 50 22 91 O Example 51 22 91 O Example 52 22 92 O Example 53 23 92 O Example 54 23 91 O Example 55 23 90 O Example 56 23 90 O Example 57 20 94 O Example 58 23 92 O Example 59 22 92 O Example 60 22 92 O Example 61 21 92 O Example 62 24 91 O Example 63 24 91 O Example 64 23 91 O Example 65 22 90 O Example 66 23 90 O Example 67 21 93 O Example 68 20 94 O Example 69 23 92 O Example 70 22 92 O Example 71 22 93 O Example 72 24 92 O Comparative Example 5 25 92 △ Comparative Example 6 25 92 x Comparative Example 7 25 89 x Comparative Example 8 25 88 x

Referring to Table 1, the release films prepared by Examples 38 to 74 maintained the same level of residual adhesion while the peel force was lowered compared to the release films prepared by Comparative Examples 5 to 8. In addition, the release films prepared by Examples 38 to 74 were suppressed in the occurrence of repelling compared to the release films prepared by Comparative Examples 5 to 8 to obtain excellent appearance.

1: (for surface energy control) organic/inorganic particles,
2: a moiety represented by Formula 1;
3: a moiety represented by Formula 2;
100: substrate, 110: release layer, 120: release film

Claims (20)

The base material and the release layer are sequentially located,
The surface energy of the release layer is 24 dyne / cm or less,
The release layer includes a polymer or copolymer including fluorinated polysiloxane and organic/inorganic particles,
The organic-inorganic particle is a release film containing moieties represented by Formula 1 and Formula 2 on its surface:
<Formula 1>
*-L ₁ -R ₁
during the ceremony,
L ₁ is selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;
R ₁ is a C1-C20 alkyl group substituted with fluorine;
* is a portion that is bonded to the particle surface.
<Formula 2>
*-L ₂ -R ₂
during the ceremony,
L ₂ is selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;
R ₂ is a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, or a substituted or unsubstituted C6-C30 cycloalkenyl group , It is selected from a substituted or unsubstituted C6-C30 bicycloalkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, and a substituted or unsubstituted C6-C30 aryl group,
* is a portion that is bonded to the particle surface. According to claim 1,
A release film in which the moiety represented by Formula 1 and Formula 2 is chemically bonded to the surface of the siloxane-based inorganic polymer particle. According to claim 1,
A release film in which the moieties represented by Formulas 1 and 2 are chemically bonded to the surface of siloxane-based inorganic polymer particles having a repeating unit structure represented by Formula 3 below:
<Formula 3>

during the ceremony,
R _a and R _b are each independently a hydrogen atom or an unsubstituted C1-C5 alkyl group,
p is an integer from 1 to 3000,
* is a moiety represented by Formula 1 and Formula 2 is bonded. According to claim 2,
A release film in which the siloxane-based inorganic polymer particles include cyclosiloxane-based polymer particles represented by Chemical Formula 4:
<Formula 4>

during the ceremony,
R' is an unsubstituted C1-C5 alkoxy group,
* is a moiety represented by Formula 1 and Formula 2 is bonded. According to claim 1,
Wherein the release layer exhibits peaks in the range of 600 to 900 cm ^-1 wavelengths and 1000 to 1250 cm ^-1 wavelengths in the IR spectrum, the release film. According to claim 1,
The thickness of the release layer is 0.03 to 3.0 ㎛, the release film. According to claim 1,
The release film having a peel force of 24 gf / 25 mm or less of the release film. According to claim 1,
A release film having a residual adhesion rate of 89% or more of the release film. adding a silicon alkoxide, a fluorine-containing silane compound, and a silane compound having a functional group to a basic solution and stirring to obtain a mixture;
centrifuging the mixture to obtain a precipitate; and
Washing and drying the precipitate to prepare organic/inorganic particles having moieties represented by Formulas 1 and 2 below on their surfaces;
The functional group is a C1-20 alkyl group, a C3-C20 cycloalkyl group, a C2-C20 alkenyl group, a C6-C30 cycloalkenyl group, a C6-C30 bicycloalkenyl group, a C1-C20 alkoxy group, and a C6-C30 group. At least one selected from C30 aryl groups,
Method for producing organic/inorganic particles for controlling surface energy, wherein the weight ratio of the fluorine-containing silane compound to the silane compound having a functional group is 1:0.05 to 1:2:
<Formula 1>
*-L ₁ -R ₁
during the ceremony,
L ₁ is selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;
R ₁ is a C1-C20 alkyl group substituted with fluorine;
* is a portion that is bonded to the particle surface.
<Formula 2>
*-L ₂ -R ₂
during the ceremony,
L ₂ is selected from a single bond and a substituted or unsubstituted C1-C5 alkylene group;
R ₂ is a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, or a substituted or unsubstituted C6-C30 cycloalkenyl group , It is selected from a substituted or unsubstituted C6-C30 bicycloalkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, and a substituted or unsubstituted C6-C30 aryl group,
* is a portion that is bonded to the particle surface. According to claim 9,
Method for producing organic/inorganic particles for controlling surface energy, wherein the fluorine-containing silane compound includes at least one of the compounds represented by A-1 to A-5 below:

A-1 A-2

A-3

A-4

A-5 According to claim 9,
Method for producing organic/inorganic particles for controlling surface energy, wherein the silane compound having the functional group includes at least one of the compounds represented by the following B-1 to B-14:

B-1 B-2

B-3

B-4 B-5

B-6 B-7

B-8 B-9

B-10 B-11

B-12 B-13

B-14 According to claim 9,
A method for producing organic/inorganic particles for controlling surface energy, wherein the organic/inorganic particles have a diameter of 1 μm or less. delete delete delete delete delete delete delete delete

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